Detergent compositions



United States Patent 3,415,752 DETERGENT COMPOSITIONS Hugh Reeves Browning, Gravesend, and Peter Carter,

Wirral, England, assignors to Lever Brothers Company,

New York, N .Y., a corporation of Maine N0 Drawing. Filed Apr. 15, 1966, Ser. No. 542,763 Claims priority, application Great Britain, Apr. 21, 1965,

Claims. (Cl. 252--96) ABSTRACT OF THE DISCLOSURE A detergent composition comprising a water-soluble organic anionic (soap or non-soap) or nonionic detergent compound, a water-soluble inorganic oxygen-releasing per compound, a fluorescer which is a derivative of 1,3-diphenyl 'A -pyrazoline, and diethylene triamine pen'taacetic acid to reduce substantially the loss of fluorescer due to the oxidative degradation thereof by the per compound.

This invention relates to detergent compositions which contain a synthetic detergent and/or a soap, an oxygenreleasing per compound, and a fluorescent brightening agent which is a derivative of 1,3-diphenyl A -pyrazoline. It is especially concerned with particulate compositions.

Although substituents in the phenyl groups of the diphenyl pyrazoline are not of importance to the mechanism of the invention the fluorescers of particular interest are of the following formula:

wherein X and Y are H, lower alkyl, aryl, CF F, --Cl, Br, CN, SO NH CO R, SO R, CO2NR1R2 0r '-SO2NR1R2 Where R is H, lower alkyl or aryl; and R and R are hydrogen, lower alkyl or aryl.

Hitherto, these detergent compositions have been unstable both in storage and in use. They have shown a loss in fluorescer content in storage and in use with consequential loss in fabric whitening effect. This loss has been found to be due to the oxidation of the fluorescer by the per compound to give the corresponding pyrazole which is then further oxidised.

This invention provides a synthetic detergent and/ or soap composition in which the loss of fluorescer is reduced.

Accordingly the present invention provides a composition comprising -a synthetic detergent and/or a soap, a brightening agent which is a derivative of 1,3-diphenyl A pyrazoline, an oxygen releasing per compound and, as an additive to reduce the loss of the pyrazoline, diethylene triamine penta acetic acid.

Particularly convenient pyraozoline fluorescers are 1- p sulphonamidophenyl) 3 (p chlorophenyl) A pyrazoline (referred to hereafter as A), l-(p-carboxymethyl phenyl) 3 (p chlorophenyl) A pyrazoline (referred to hereafter as B) and 1-(m-chlorophenyl)-3- p-acety laminophenyl) A pyrazoline (referred to hereafter as compound C). Such fluorescers may be .present in the detergent compositions at concentrations varying from 0.01% to 0.05%.

Suitable per compounds are alkali metal perborates and alkali metal per carbonates, e.g. sodium perborate and sodium percarbonate. Hydrogen peroxide may be used in liquid formulations.

These may be present in the detergent compositions at concentrations varying from l-50%, preferably 10-20% by weight of the total composition.

The concentration of diethylene triamine pent-a acetic acid (DETPA) to be used in the compositions depends on the degree of stabilisation required of the composition, the amount and stability of the per compound present and the storage conditions likely to be encountered.

The compositions lose their fluorescer more rapidly when stored under climatic conditions of elevated temperature and humidity and consequently products to be stored under such conditions may require a higher level of DETPA than those to be stored under milder conditions. Useful levels of DETPA range from 0.01% to 2% on the final composition. The levels usually found to be successful are 0.ll% by weight of the composition.

DETPA has the advantage of compatibility with detergent compositions and does not affect the physical properties or the washing performance of the detergent composition to which it is added.

The synthetic detergent, if present, is conveniently an anionic compound, for example an alkyl aryl sulphonate, especially sodium dodecyl benzene su lphonate, an alkyl sulphate, or an alkyl glyceryl ether sulphonate. This is present in amount varying from 5 to 50% by weight of the composition. With the higher amounts of synthetic detergent, less additive may be found necessary for adequate stabilisation to storage.

A nonionic detergent may be used for example, an alkylene oxide condensate of an alcohol or phenol, such as tallow alcohol/9 ethylene oxide or nonyl phenol/9 ethylene oxide condensates.

In compositions in which the active is provided by soap, suitable soaps are the sodium, potassium or ammonium salts of tallow fatty acids or coconut fatty acids or the blends customary in the production of particulate soap-based products.

These are present in amount 5 to of the total composition.

The invention is also concerned with compositions in which both synthetic detergent and soap are present.

The usual ingredients of detergent compositions may be present, viz. builders, perfume, etc. Further fluorescer components may be added, e.g. the cotton fluorescers of the triazinyl stilbene type.

The effect of the DETPA in reducing the loss of fluorescer from a typical perborated detergent composition is shown below.

Example 1 Detergent products were prepared from a slurry of 200 g. active detergent (sodium dodecyl benzene sulphonate), 350 g. of sodium t-ripolyphosphate, 270 g. of builder salt and 400 g. of water. To this slurry was added fluorescer, and DETPA in the amounts shown in the following table. The resultant slurry was then drum dried and a portion of each power except the control portion was dry mixed with 10% sodium perborate. The powders were stored in laminated cardboard containers in a room held at 20 C. and relative humidity. Periodically the powders were removed and their fluorescer contents were estimated by washing a piece of non-fluorescent nylon fabric in an aqueous solution of the powder for 5 minutes at 60 C. From the fluorescence measurements of the fabrics it was possible to estimate the amount of fluorescer remaining in the stored powder. The results obtained for these powders is given below and compared with a powder without DETPA.

TABLE I Percent A remaining on storage Percent by weight of total composition days 14 days 38 days 70 days 0.08% A (as control) 100 96 95 90 0.08% A, 10.0% sodium perborate 100 68 26 1 0.08% A, 10.0% sodium perborate, 1.0% DETPA 100 100 93 90 Example 2 0 Similar results were obtained from powders of the foregoing slurry, spray-dried and stored at C. and 90% RH, as shown below:

TABLE II Percent original B remain- Percent by weight of total composition ing on storage 0 days 8 days 14 days 0.025% B 100 95 0.025% B, 10.0% sodium perborate 100 50 12 0.025% B 10.0% sodium perborate, 0.10 DET 100 89 74 Example 3 Under less humid storage conditions 23 C. and 70% RH. the decomposition rates of the unstabilised product was slower but a similar stabilising effect was observed as follows:

TABLE III Percent B remaining on storage 0 days 28 days 70 days 160 days .025 B 100 98 98 89 .025 B, 10.0% sodium porborate 100 68 30 9 .025 B, 10.0% sodium perborate 0.10 DETPA 100 95 86 75 Further examples of fluoreseer stabilisations' in spray dried products based on the above mentioned slurry formulation:

Example 4 TABLE IV Percent B remaining on storage at 23 0., 70% RH.

0 days 70 days 160 days 0.065% B 100 100 95 0.065% B, 10% sodium perborate 100 34 0.065% B, 10% sodium perborate, 100 92 84 Example 5 TABLE V [Storage conditions 23 0., R.H.]

Percent 0 remaining on storage 0 days 28 days 70 days .025% C 100 100 97 .025% C, 35% perborat 100 35 10 .025% O, 35% sodium perborate, 100 92 Example 6 TABLE VI Percent B remainjn after storage at 23 0., 70%? RH.

0 days 28 days 70 days 0.065% B 100 98 98 0.065% B, 50% sodium perborate 100 72 60 0.065% B, 5.0% sodium perborate, 0.1% DETPA 100 95 92 Example 7 TABLE VII Percent B remainin after storage at 23 0., 70 o R.H.

Percent B remaining after storage at 23 0.,

0 days 14 days 25 days 67 days 82 days 08% B sodium perborate 0. 0.08% B, 0.08% B, 10% sodium perborate, 0.5% DETPA Other detergent compositions to which DETPA can be added according to the invention are typified by the following examples:

in Table IX in which its stabilisation eifect is compared with the effects of EDTA and Trilon A (nitrilo triacetic acid), using the spray dried slurry of Example 2.

TABLE IX Storage conditions 23 0., %R.H

0 days 70 days 100 days 0.025% A 100 98 9s 0.025% A, 10% sodium perborate 100 20 12 0.025% A, 10% sodium perborate, 0.5% DETPA 100 91 87 0.025% A, 10% sodium perborate, 0.5% EDTA. 100 80 70 0.025% A, 10% sodium perborate, 0.5% Trilon A... 100 32 17 Example 9 Example 13 Sodium dodecyl benzene sulphonate A typical liquid formulation is: Anhydrous soap 4 Percent Sodium tripolyphosphate 25 Sodium dodecyl benzene sulphonate 10.0 Sodium sulphate 10 Potassium pyrophosphate 20.0 Sodium silicate 8 Sodium xylene sulphonate 4.0 Sodium perborate 15 Fluorescer A 0.03 Fluorescer B 0.08 DETPA 0.20 DETPA 0.2 Hydrogen peroxide 4.0

Water, perfume, cotton substantive fluorescer balance.

Example 10 Anhydrous soap Sodium carbonate Sodium silicate 8 Sodium perborate 10 Fluorescer A 0.03

DETPA 1 0.1

Water, perfume, cotton substantive fluorescer balance.

That DETPA is effective to a surprising degree in bringing about such stabilisations is illustrated by the results In the foregoing examples, potassium perborate or percarbonate may replace the sodium perborate or percarbonate respectively.

What is claimed is:

1. A detergent composition consisting essentially of (1) a water-soluble organic detergent compound selected from the group consisting of (a) from about 5% to about 50% by weight of (a a nonionic detergent and (a an anionic non-soap detergent and (b) from about 5% to about 75% by weight of a soap, (2) from about 1% to about 50% by weight of a water-soluble inorganic oxygenreleasing per compound, (3) from about 0.01% to about 0.5% by weight of a fluorescer which is a derivative of l,3-diphenyl-A -pyrazoline selected from the group consisting of l-(p-sulphonamidophenyl)-3-(p-chlorophenyl)- A -pyrazoline, l-(p-carboxymethyl phenyl)-3-(p-chloropheny1)-A -pyrazoline and l-(m-chlorophenyl)v3-(p-acetylaminophenyl)-A -pyrazoline, and (4) from about 0.01% to about 2% by weight of diethylene triamine pentaacetic acid.

2. The detergent composition as defined by claim 1 wherein the water-soluble organic detergent compound is selected from the group consisting of nonionic deter- 5. The detergent composition as defined by claim 1 wherein the diethylene triamine pentaacetic acid is present in an amount from about 0.1% to about 1% by weight.

5 References Cited UNITED STATES PATENTS 3,357,988 12/1967 Hausermann et a1. 252-99 XR MAYER WEINBLA'IT, Primary Examiner.

U.S. Cl. X.R. 25295, 94, 186, 99; 8111 

